Iridium-Based High-Sensitivity Oxygen Sensors and Photosensitizers with Ultralong Triplet Lifetimes

The photophysics of a series of bichromophoric molecules featuring an intramolecular triplet energy transfer between a triscyclometalated iridium­(III) complex and covalently linked organic group are studied. By systematically varying the energy gap (0.1–0.3 eV) between the donor (metal complex) and acceptor (pyrene unit), reversible triplet energy transfer processes with equilibrium constant <i>K</i> ranging from ca. 500 to 40 000 are established. Unique photophysical consequences of such large <i>K</i> values are observed. Because of the highly imbalanced forward and backward energy transfer rates, triplet excitons dominantly populate the acceptor moiety in the steady state, giving rise to ultralong luminescence lifetimes up to 1–4 ms. Because the triscyclometalated Ir and triplet pyrene groups both impart relatively small nonradiative energy loss, decent phosphorescence quantum yields (Φ = 0.1–0.6) are attained in spite of the exceptionally prolonged excited states. By virtue of such precious combination of long-lived triplet state and high Φ, these bichromophoric molecules can serve as highly sensitive luminescent sensors for detecting trace amount of O₂ and as potent photosensitizers for producing singlet oxygen even under low-oxygen content conditions